Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_sr244 _database_code_CSD 181122 _journal_coden_Cambridge 186 loop_ _publ_author_name _publ_author_address 'Sylvie L. Renard' ; School of Chemistry University of Leeds Leeds LS2 9JT UK ; 'Julie Fisher' ; School of Chemistry University of Leeds Leeds LS2 9JT UK ; 'Colin A. Kilner' ; School of Chemistry University of Leeds Leeds LS2 9JT UK ; 'Mark Thornton-Pett' ; School of Chemistry University of Leeds Leeds LS2 9JT UK ; 'Terence P. Kee' ; School of Chemistry University of Leeds Leeds LS2 9JT UK ; # 1. SUBMISSION DETAILS _publ_contact_author_name 'Dr T Kee' _publ_contact_author_address ; School of Chemistry University of Leeds Leeds LS2 9JT UK ; _publ_contact_author_phone '+44 (0)113 2336423' _publ_contact_author_fax '+44 (0)113 2336565' _publ_contact_author_email marktp@chem.leeds.ac.uk _publ_requested_journal 'J. Chem. Soc., Dalton Trans.' _publ_contact_letter ; The following set of data is supplementary data for the crystal structure included in the paper, details of which are given below ; #======================================================================= # 2. TITLE AND AUTHOR LIST _publ_section_title ; On the mechanisms of degenerate halogen exchange in phosphorus(III) esters ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H22 Cl N4 P' _chemical_formula_weight 408.86 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x+1/2, -y, z+1/2' _cell_length_a 7.4730(3) _cell_length_b 15.6217(9) _cell_length_c 17.9713(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2097.99(18) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needle _exptl_crystal_colour colourles _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.294 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 856 _exptl_absorpt_coefficient_mu 0.273 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9398 _exptl_absorpt_correction_T_max 0.9892 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 15 degree phi range. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9792 _diffrn_reflns_av_R_equivalents 0.0627 _diffrn_reflns_av_sigmaI/netI 0.0836 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 3.46 _diffrn_reflns_theta_max 26.00 _reflns_number_total 4005 _reflns_number_gt 3045 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP3 for Windows (Farrugia, 1997)' _computing_publication_material 'WC (Thornton-Pett, 2000)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+0.9760P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.004(3) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.08(10) _refine_ls_number_reflns 4005 _refine_ls_number_parameters 254 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0844 _refine_ls_R_factor_gt 0.0528 _refine_ls_wR_factor_ref 0.1101 _refine_ls_wR_factor_gt 0.0962 _refine_ls_goodness_of_fit_ref 1.097 _refine_ls_restrained_S_all 1.097 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group P1 P -0.03426(12) 0.15034(7) 0.77627(5) 0.0408(3) Uani 1 1 d . . . Cl1 Cl 0.18617(12) 0.23276(6) 0.81754(6) 0.0492(3) Uani 1 1 d . . . C1 C -0.2848(4) 0.1553(2) 0.87822(18) 0.0384(8) Uani 1 1 d . . . H1 H -0.3736 0.1111 0.8621 0.046 Uiso 1 1 calc R . . C2 C -0.1229(5) 0.1092(2) 0.9101(2) 0.0409(9) Uani 1 1 d . . . H2 H -0.0421 0.1531 0.9328 0.049 Uiso 1 1 calc R . . C3 C -0.1792(6) 0.0470(2) 0.97087(19) 0.0440(9) Uani 1 1 d . . . H3A H -0.0729 0.0179 0.9918 0.053 Uiso 1 1 calc R . . H3B H -0.2607 0.0031 0.9503 0.053 Uiso 1 1 calc R . . C4 C -0.2748(5) 0.0986(2) 1.0316(2) 0.0465(9) Uani 1 1 d . . . H4A H -0.3213 0.0587 1.0698 0.056 Uiso 1 1 calc R . . H4B H -0.1872 0.1369 1.0561 0.056 Uiso 1 1 calc R . . C5 C -0.4289(5) 0.1521(3) 1.00156(19) 0.0455(9) Uani 1 1 d . . . H5A H -0.4786 0.1874 1.0424 0.055 Uiso 1 1 calc R . . H5B H -0.5248 0.1134 0.9839 0.055 Uiso 1 1 calc R . . C6 C -0.3726(5) 0.2107(2) 0.9378(2) 0.0420(9) Uani 1 1 d . . . H6A H -0.4784 0.2405 0.9170 0.050 Uiso 1 1 calc R . . H6B H -0.2870 0.2544 0.9559 0.050 Uiso 1 1 calc R . . N1 N -0.2149(4) 0.19772(19) 0.81137(16) 0.0403(7) Uani 1 1 d . . . C7 C -0.3326(5) 0.2522(2) 0.7657(2) 0.0462(9) Uani 1 1 d . . . H7A H -0.4536 0.2264 0.7650 0.055 Uiso 1 1 calc R . . H7B H -0.2871 0.2521 0.7140 0.055 Uiso 1 1 calc R . . C8 C -0.3486(4) 0.3442(2) 0.79161(19) 0.0409(8) Uani 1 1 d . . . C9 C -0.2157(5) 0.3848(3) 0.8315(2) 0.0491(10) Uani 1 1 d . . . H9 H -0.1090 0.3546 0.8432 0.059 Uiso 1 1 calc R . . C10 C -0.2351(5) 0.4679(3) 0.8546(2) 0.0522(10) Uani 1 1 d . . . H10 H -0.1415 0.4949 0.8817 0.063 Uiso 1 1 calc R . . C11 C -0.3915(5) 0.5130(3) 0.8387(2) 0.0464(9) Uani 1 1 d . . . C12 C -0.5245(5) 0.4740(3) 0.7960(2) 0.0549(11) Uani 1 1 d . . . H12 H -0.6292 0.5049 0.7827 0.066 Uiso 1 1 calc R . . C13 C -0.5032(5) 0.3904(3) 0.7733(2) 0.0529(10) Uani 1 1 d . . . H13 H -0.5946 0.3637 0.7448 0.063 Uiso 1 1 calc R . . C14 C -0.4142(6) 0.5995(3) 0.8642(2) 0.0543(11) Uani 1 1 d . . . N14 N -0.4333(5) 0.6689(3) 0.8833(2) 0.0691(11) Uani 1 1 d . . . N2 N -0.0337(4) 0.07487(18) 0.84255(15) 0.0380(7) Uani 1 1 d . . . C15 C 0.1353(5) 0.0279(2) 0.8535(2) 0.0466(9) Uani 1 1 d . . . H15A H 0.2062 0.0572 0.8924 0.056 Uiso 1 1 calc R . . H15B H 0.2051 0.0299 0.8067 0.056 Uiso 1 1 calc R . . C16 C 0.1100(5) -0.0647(2) 0.8758(2) 0.0418(9) Uani 1 1 d . . . C17 C 0.2463(5) -0.1056(3) 0.9157(2) 0.0499(10) Uani 1 1 d . . . H17 H 0.3490 -0.0740 0.9305 0.060 Uiso 1 1 calc R . . C18 C 0.2333(6) -0.1909(3) 0.9337(2) 0.0557(11) Uani 1 1 d . . . H18 H 0.3274 -0.2183 0.9600 0.067 Uiso 1 1 calc R . . C19 C 0.0832(5) -0.2363(3) 0.9133(2) 0.0468(9) Uani 1 1 d . . . C20 C -0.0544(6) -0.1968(3) 0.8744(2) 0.0512(10) Uani 1 1 d . . . H20 H -0.1589 -0.2280 0.8614 0.061 Uiso 1 1 calc R . . C21 C -0.0383(6) -0.1113(3) 0.8548(2) 0.0502(9) Uani 1 1 d . . . H21 H -0.1302 -0.0847 0.8265 0.060 Uiso 1 1 calc R . . C22 C 0.0702(6) -0.3259(3) 0.9323(2) 0.0538(11) Uani 1 1 d . . . N22 N 0.0623(5) -0.3967(2) 0.9472(2) 0.0674(11) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 P1 0.0400(5) 0.0438(6) 0.0387(5) -0.0003(5) 0.0040(4) 0.0015(4) Cl1 0.0384(4) 0.0492(6) 0.0599(6) 0.0015(5) 0.0033(5) -0.0055(4) C1 0.0343(17) 0.041(2) 0.0396(18) -0.0017(16) 0.0043(15) -0.0042(16) C2 0.0397(18) 0.040(2) 0.043(2) -0.0033(17) 0.0078(17) -0.0011(16) C3 0.058(2) 0.035(2) 0.0395(18) 0.0026(16) 0.0085(19) 0.0003(18) C4 0.053(2) 0.045(2) 0.041(2) 0.0034(17) 0.0079(19) -0.0065(18) C5 0.048(2) 0.048(2) 0.0403(18) -0.0056(18) 0.0113(17) -0.0081(19) C6 0.0357(17) 0.048(2) 0.0423(19) 0.0006(17) 0.0028(16) 0.0047(16) N1 0.0337(14) 0.0458(17) 0.0414(16) 0.0070(14) 0.0015(14) 0.0029(12) C7 0.0379(18) 0.061(3) 0.0395(19) 0.0022(18) -0.0041(17) 0.0047(17) C8 0.0394(18) 0.044(2) 0.0396(19) 0.0101(17) 0.0024(16) 0.0000(17) C9 0.046(2) 0.050(2) 0.052(2) 0.0059(18) -0.010(2) 0.0091(18) C10 0.050(2) 0.056(3) 0.051(2) 0.008(2) -0.009(2) 0.0062(19) C11 0.049(2) 0.041(2) 0.049(2) 0.0141(17) 0.0039(19) 0.0044(18) C12 0.0391(19) 0.053(3) 0.073(3) 0.020(2) 0.001(2) 0.0031(18) C13 0.042(2) 0.053(3) 0.063(2) 0.014(2) -0.008(2) 0.0008(17) C14 0.053(3) 0.053(3) 0.057(2) 0.009(2) 0.001(2) 0.008(2) N14 0.068(3) 0.061(3) 0.078(3) 0.002(2) -0.005(2) 0.014(2) N2 0.0389(15) 0.0362(17) 0.0388(15) -0.0002(13) 0.0061(14) 0.0022(13) C15 0.042(2) 0.041(2) 0.056(2) -0.0016(19) 0.0026(18) 0.0054(17) C16 0.0438(19) 0.037(2) 0.045(2) -0.0060(17) 0.0032(17) 0.0058(17) C17 0.050(2) 0.045(2) 0.055(2) -0.0010(19) 0.003(2) 0.0054(18) C18 0.061(3) 0.054(3) 0.051(2) -0.003(2) -0.007(2) 0.017(2) C19 0.061(2) 0.037(2) 0.043(2) -0.0056(18) 0.0040(19) 0.0060(19) C20 0.054(2) 0.046(2) 0.054(2) -0.0052(19) -0.004(2) 0.004(2) C21 0.052(2) 0.043(2) 0.055(2) 0.0012(19) -0.005(2) 0.0073(19) C22 0.061(3) 0.047(3) 0.053(2) -0.006(2) -0.002(2) 0.009(2) N22 0.081(3) 0.042(2) 0.079(3) 0.0045(19) -0.007(2) 0.009(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag P1 N1 1.664(3) . ? P1 N2 1.676(3) . ? P1 Cl1 2.2184(14) . ? C1 N1 1.469(4) . ? C1 C2 1.520(5) . ? C1 C6 1.526(5) . ? C2 N2 1.485(4) . ? C2 C3 1.522(5) . ? C3 C4 1.533(5) . ? C4 C5 1.522(5) . ? C5 C6 1.526(5) . ? N1 C7 1.473(4) . ? C7 C8 1.516(5) . ? C8 C9 1.379(5) . ? C8 C13 1.402(5) . ? C9 C10 1.371(5) . ? C10 C11 1.395(5) . ? C11 C12 1.395(5) . ? C11 C14 1.436(6) . ? C12 C13 1.377(6) . ? C14 N14 1.147(5) . ? N2 C15 1.474(4) . ? C15 C16 1.513(5) . ? C16 C21 1.379(5) . ? C16 C17 1.400(5) . ? C17 C18 1.375(6) . ? C18 C19 1.377(6) . ? C19 C20 1.389(5) . ? C19 C22 1.443(6) . ? C20 C21 1.386(5) . ? C22 N22 1.139(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 P1 N2 92.61(14) . . ? N1 P1 Cl1 102.56(11) . . ? N2 P1 Cl1 99.72(11) . . ? N1 C1 C2 103.8(3) . . ? N1 C1 C6 118.1(3) . . ? C2 C1 C6 110.3(3) . . ? N2 C2 C1 102.7(3) . . ? N2 C2 C3 118.7(3) . . ? C1 C2 C3 110.6(3) . . ? C2 C3 C4 107.7(3) . . ? C5 C4 C3 112.8(3) . . ? C4 C5 C6 112.8(3) . . ? C1 C6 C5 107.7(3) . . ? C1 N1 C7 120.3(3) . . ? C1 N1 P1 113.5(2) . . ? C7 N1 P1 122.0(2) . . ? N1 C7 C8 115.1(3) . . ? C9 C8 C13 118.6(4) . . ? C9 C8 C7 122.6(3) . . ? C13 C8 C7 118.8(3) . . ? C10 C9 C8 121.1(4) . . ? C9 C10 C11 120.3(4) . . ? C10 C11 C12 119.3(4) . . ? C10 C11 C14 120.5(4) . . ? C12 C11 C14 120.2(4) . . ? C13 C12 C11 119.7(4) . . ? C12 C13 C8 120.9(4) . . ? N14 C14 C11 178.8(5) . . ? C15 N2 C2 117.1(3) . . ? C15 N2 P1 116.6(2) . . ? C2 N2 P1 109.0(2) . . ? N2 C15 C16 113.8(3) . . ? C21 C16 C17 119.0(4) . . ? C21 C16 C15 122.2(3) . . ? C17 C16 C15 118.7(3) . . ? C18 C17 C16 120.7(4) . . ? C17 C18 C19 119.6(4) . . ? C18 C19 C20 120.5(4) . . ? C18 C19 C22 119.4(4) . . ? C20 C19 C22 120.1(4) . . ? C21 C20 C19 119.5(4) . . ? C16 C21 C20 120.6(4) . . ? N22 C22 C19 179.1(5) . . ? _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 0.322 _refine_diff_density_min -0.209 _refine_diff_density_rms 0.047